CN1159574A - Photochromism explosure meter - Google Patents
Photochromism explosure meter Download PDFInfo
- Publication number
- CN1159574A CN1159574A CN96123411A CN96123411A CN1159574A CN 1159574 A CN1159574 A CN 1159574A CN 96123411 A CN96123411 A CN 96123411A CN 96123411 A CN96123411 A CN 96123411A CN 1159574 A CN1159574 A CN 1159574A
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- Prior art keywords
- camera
- photochromic
- luo
- phenoxazine
- alkyl
- Prior art date
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- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 20
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Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
- G03B17/00—Details of cameras or camera bodies; Accessories therefor
- G03B17/18—Signals indicating condition of a camera member or suitability of light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/48—Photometry, e.g. photographic exposure meter using chemical effects
- G01J1/50—Photometry, e.g. photographic exposure meter using chemical effects using change in colour of an indicator, e.g. actinometer
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
- G03B2219/00—Cameras
- G03B2219/02—Still-picture cameras
- G03B2219/04—Roll-film cameras
- G03B2219/045—Roll-film cameras adapted for unloading the film in the processing laboratory, e.g. disposable, reusable or recyclable cameras
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/163—Radiation-chromic compound
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Structure And Mechanism Of Cameras (AREA)
Abstract
The invention relates to a light sensing device comprising a spironaphthoxazine dispersed in a layer of gelatin on a base material.
Description
The present invention relates to a kind of device of the intensity of pilot light intuitively.The present invention relates to the device that need glisten when showing the photographic film exposure particularly.
Expensive electronic flash camera has metraster or other are contained in the exposure measuring device that can read scene environment light quantity being shot in the camera and excite flasher automatically when the lighting condition of reading is not enough to produce effective exposure.
At some more cheap cameras, as Eastman Kodak Company and Fuji PhotoFilm Co., once use that Ltd. produces or single use in the camera.Flasher is manual, and generally the outer actual switch of camera body controls by being contained in, and this switch can excite flasher when pressing the shutter release key.Before taking a certain image, common user must judge that amount of ambient light determines whether using flasher by observing.Use flashlamp inadequately or do not use flashlamp will produce inharmonic result, cause being discontented with of consumer.
In other cases, as when using indoor light source, should guide or remind the user to be ready to flasher before filmed image, the photo majority of taking under this condition all need be used flashlamp.
Be disclosed in photosensitive device and reference instrument that the Japanese Kokai 4-213031 on August 4th, 1992 has described to be installed on the disposable camera.Photosensitive device comprises a kind of photosensitive material of this material variable color when incident UV radiation shines on this material.The color of photosensitive device and the color of reference instrument are relatively come measuring light illumination, and whether decision should take pictures then.
The UV-photosensitive device that is disclosed in 1992 Augusts 4, purpose Japanese Kokai 4-213029 described to use with reference instrument.One piece of finger ring that this reference instrument is worn for the user, according to the illuminance that it shows, UV photosensitive device changes colour contrasts with this and reference instrument.
U.S.Patent 4,804, and 992 have described the indicating device that is used for camera view finder, and it comprises will whether causing the result of inappropriate exposure to offer the photochromic material of visual detector according to special scene brightness.
The Japanese Kokai 5-142700 that is disclosed on June 11st, 1993 has described the purposes of the photochromic material on the single use camera, and according to the installation site of this material, it both can be used as the luminance brightness detecting device and also can be used as the camera lens color filter.
Japanese patent application 3-196673, JP 01-038283, JP 63-296871 and JP 01-011185 disclose sightless ink or coating.Luo oxazine (spirooxazines) is disclosed as photochromic material.
Up to the present, still need a kind of more effective color change system, thereby no longer need the reference measurement of difficulty.In addition, still need the solar sensor of photographing, thereby the color of the difficulty that no longer need be undertaken by the people who uses camera occasionally relatively.
An object of the present invention is to make single to use camera to take better photo.
Another object of the present invention is to provide a method of rationally using flashlamp for single uses the camera user.
Stack up, these purposes of the present invention can comprise the photosensitive device that is scattered in the photochromic chemical substance in the hydrophilic colloid and finish by providing.
Preferred photosensitive device comprises the Luo phenoxazine (spironaphthoxazine) that is scattered in the gelatin layer.
Compare the present invention with former solar sensor and have many advantages.Sensor conversion of the present invention is used the required light quantity of photographic film exposure in the camera at single.In addition, optical sensor of the present invention can provide the variation clearly from a kind of color to the diverse color of another kind in a short period of time.The variation of this indicating device is so fast, just knows whether need flashlamp when taking so that the camera user need not to wait for.In addition, device manufacturing of the present invention and good elasticity is arranged.Another advantage of solar sensor of the present invention is an indefatigability, still can accurately indicate exposure after repeatedly using.These advantages and other advantages will be become clear by following description.
Fig. 1 is the figure of element of the present invention.
Fig. 2 is the xsect sectional drawing of the 2-2 line of Fig. 1 element of the present invention.
Fig. 3 is the top view with element of the present invention of uv absorption layer.
Fig. 4 is the xsect sectional drawing of the 4-4 line among Fig. 3.
Fig. 5 is to use the skeleton view of the camera of element of the present invention.
Fig. 6 is to use the skeleton view of camera of the band flasher of element of the present invention.
Thereby the invention provides a kind of element that change color obtains the gratifying photo of exposure that when exposure under a certain amount of sight, produces significantly rapidly. Element of the present invention can resist maloperation usually, and at camera, particularly disposable camera keeps stable in the scope of shooting condition.
Fig. 1 is the top view of the circular indicator elment of the present invention.
Fig. 2 is the cross section sectional drawing of element 10 2-2 along the line. This element comprises the hyaline layer 12 of top hard and according to the photoactive layers 14 of daylight variation of exposure color. Sheet base paper layer 16 has been installed between polymer waterproof membrane 18 and 22. Element shown in Figure 2 has also been installed the adhesive phase 24 that is coated with the ply of paper 26 that can tear off. After this ply of paper is torn off, can element of the present invention be fixed on suitable substrate such as the disposable camera by adhesive phase 24. The material of preferred layer 12 and 14 is hydrophilic colloid, and such as gelatin, this can make the photochromic compound of the present invention that is dispersed in the gelatin layer 14 promptly react. Layer 12 is generally the hydrophilic colloid with the crosslinking agent that forms rigid surface. Layer 12 is not essential to the invention, is desirable but will fill hard protective layer with the wearability that improves element of the present invention.
The element of the present invention 30 that Fig. 3 shows has engraved mark 32 and 34, when component exposure of the present invention in daylight lower time, this mark demonstrates the words and phrases directly perceived that can read. When component exposure shown in Figure 3 in daylight lower time, 32 and 34 is dimmed. What Fig. 4 showed is that element 30 is along the cross section sectional drawing of 4-4 line. As shown in the figure, this element comprises UV absorption layer 36, glutoid layer or other hydrophilic colloid layers 12. UV absorption layer 36 covers on the photochromic layer 14, between photochromic layer 14 and sun-exposed above between, away from sheet base 16. The photochromic layer 14 that contains photochromic material such as Luo phenoxazine of the present invention can colouredly change in zone 38,42 and 44, at those zone markers 32 and 34 by the ultraviolet exposure of the daylight by the breach place in the layer 34. Identical in sheet base paper and the element 10. Element 30 is not installed adhesive phase, can be by independently adhesive installation in the use.
Fig. 5 illustrates that single uses camera 50. Camera 50 has been installed and has a little been taken the photograph switch 52, film advancing wheel 54, and frame indicator 56. Camera lens 60 is positioned at the front of camera, and view finder 58 also in front. What be positioned at camera top 61 is whether suitable three indicators 62,64 of indication exposure, and 68. The element of the present invention that the 68th, Fig. 4 shows, when light quantity satisfied shooting condition, camera operator can be seen " OK " wherein. The printing type face that indicator 62 equipment rings show, when the indication equivalent showed " OK ", shooting can be carried out. Indicator 64 is used for contrasting low-light level model border, and at this moment indicator of the present invention is lily. The user of camera can compare indicator 68 of the present invention, if mark 66 occurs, just light satisfies shooting as can be known. If mark 66 does not occur, still be transparent,, camera knows that insufficient light is to take just using.
Illustrated among Fig. 6 is camera 70.Camera 70 is that the single of band flasher uses camera.This camera also has the function of flash of light camera except that the feature with camera 50.It is in running order to preset lamp 72 indication flashlamp 74.Hold the flashlight charging control lever, when Flash ready, lamp 72 is luminous.Indicating device 68 of the present invention is used to indication in the mode identical with " OK " 62; As " OK " in 68, occurring, then do not need to use flashlamp.The comparison object of reference 64 on next door is used for showing: if indicator 66 is white, then should use flashlamp.
The sheet base paper of coating photochromic compound of the present invention can be that the stable any suitable material of supporting and combining with the hydrophilic colloid layer that is loaded with photochromic compound can be provided.Preferable material is the colour paper sheet base that is used to photograph.These materials are the paper that the two sides scribbles polyethylene layer.Further, they also contain reflecting material usually, perhaps at polyethylene layer 18, perhaps as the separating layer between gelatin layer 14 and the polyethylene film 18.The material that typically is used to reflect is a titania.Although also can use other white reflecting material.Use blueness that the reflection base can improve the spiral shell phenoxazine dyestuff that is exposed under the ultraviolet light with in dark reaction between the white of visible base when becoming to hang down under the light quantity environment transparence in this dyestuff.
The single that is preferably used for of the photochromic element of the present invention uses camera.But this element also can be installed in not the reusable camera of the low price that the light activated element that is used to control exposure is installed.Further, element of the present invention also is used in famous, watches from a height or a distance the place indicia on the outdoor scene of photography such as the valley or in the mountain, in addition, is used in other area as photograph is memorized in the recreation ground candid photograph.In these zones, the photochromic element of the present invention can be placed has the sign that instructs below: if round dot is white, insufficient light is described to carry out general shooting, if indicating device has color, then can carries out general shooting.
Other parts of the present invention comprise the photochromic device of the present invention are applied to existing camera as retrofit device.There is a large amount of cameras not have recognition function.Apparatus of the present invention can be connected on these cameras, it be had measure the function whether light satisfies shooting.As another part of invention, photochromic device of the present invention is not to use the method for shaping but forms the mark of aforementioned part by printing.
Preferred photochromic compound of the present invention produces change color rapidly when luminance brightness is suitable for the shooting of single use camera.Suitable The compounds of this invention comprises fulgide ， Luo oxazine, and spiro-pyrans.The Luo phenoxazine that preferably has outstanding fatigue properties.Most preferred 5-chloro-1,3-dihydro-1,3,3-trimethyl spiral shell-[2H-indoles-2,3 '-(3H) fen (2,1-b)-(1,4) oxazine] and 1,3-dihydro-1,3,3-trimethyl spiral shell-[2H-indoles-2,3 '-(3H) fen (2,1-b)-(1,4) oxazine] can be in optimization formula to the indication of about 45-footlambert's incident light generation change color.This is suitable for typical single and uses the aperture of camera with about f/10, uses 400 degree films, takes exposure 1/100 second shutter speed.Other photochromic compound or other prescriptions are applicable to produce change color under more or less different light intensity.Optionally, if above-mentioned preferred compound is used for low-speed film as 100 degree films, can settles filter dye or this dyestuff to be dispersed in the spiral shell phenoxazine of the present invention so in the above, thereby under highlight strength, change color take place.
Have been found that the speed that the Luo phenoxazine of the present invention that is formulated in the photosensitive type disperse system can be very fast produces change color.In general, suitable complete transformation period should be less than one minute.But preferred transformation period should be less than for 10 seconds.Having been found that preferred material only is exposed under the daylight just can to produce basically in the several seconds changes completely.It is to be noted Luo phenoxazine of the present invention only to the UV radiation sensitivity, therefore, do not find its practical use the tungsten light that is suitable for taking in indoor indication.Yet, for the once use camera of the film of the usual speed that 400ASA is housed, almost always need flashlamp during pickup, therefore, photochromic indicator can obtain correct reaction.
The light shield layer that the block sunlight that the present invention uses arrives Luo phenoxazine dyestuff preferably uses UV absorbers to form, because these materials are transparent.But, also can use the daylight filter dye.Known such filter dye is used for photographic negative.Can or use the frisket printing beam to carry out the printing of the photochromic material of all styles of by conventional method such as printing, spray printing.Printing process is known in this area.Preferred UV absorption compound blocks ink for the UV that some for example contain among the Tinuvins of Ciba Geigy.
The photochromic compound of any appropriate amount all can be applied in the photochromic element of the present invention.When having found with the coating of preferred Luo phenoxazine compound-material, suitable amount is every square feet about 3 to about 150 millimeters.Preferred amount is 10 to 15 milligrams every square feet, and at this moment photochromic material has good color under daylight, is transparence when being in low-light level light following time.
A preferred form of the present invention comprises photochromic material purposes as light meter on single use camera.Can use when obtaining correct exposure on the camera at the single of fixed aperture and shutter speed when the incident light level, the light meter variable color becomes obviously symbol or word, indicates photographer will obtain an acceptable photo of quality.
Therefore in photochromic material, two or more have different absorption spectrums and have between the chemical species of different colours and have balance.In sketch (formula 1), absorption incident photoconduction causes species (A) and is transformed into another kind (B) by photochemical method, and the result produces change color.Second kind (B) or be returned to first kind (A) by heat treating process or by photochemical method.To some application, for example, laser intensity table, or optical computer memory storage can be expected to finish reversed reaction (A ← B) separately by photochemistry.For the present invention, preferred reversed reaction mainly or fully is a thermal response, so that reduce under the situation that is not enough to take in luminance brightness, and the blackout that causes by photoconduction.
In simple (imaginary) embodiment (Fig. 1), the character of photochromic compound depends on: the absorption spectrum of two kinds, photochemically reactive efficient, and thermal velocity constant K-1.Absorption spectrum is described the wavelength that drives photochemically reactive light, the color of two kinds, and the change color that is produced, and (to a certain extent) two kinds produce absorption density.Preferred compound only absorbs UV light, thereby is colourless when being in the A type, and very dark color is arranged when being in Type B." formation of intensity produces the required luminance brightness of visible change color (light sensitivity) to photochemically reactive efficient, and being exposed to the speed that produces change color under the enough light has contribution to color.Hot reversed reaction velocity constant (K-1) speed that compound fades when removing light source (fade rates), it is the coefficient that obtains under maximum intensity.Velocity constant depends on employed photochromic compound, depends on the environment of compound simultaneously to a great extent.For example, fade constant than much bigger in hard polymeric material when compound is dissolved in mobile solvent, the constant that fades simultaneously also depends on the character of medium.Velocity constant also depends on temperature to a great extent.Every rising approximately increases three coefficients for 10 ℃.
The application desires to achieve success, and photochromic material must satisfy several requirements.It at first is the light sensitivity of material.Change color must take place under suitable light intensity.The color density of material production must be easy to the camera operator identification.Color forms must be fast, and fading rate also must be fast, and when being lower than the required level of film correct exposure with convenient light intensity, photographer can in time know.Because color fading reaction is a thermal response, so it depends on temperature, and all These parameters can be considered to the dependence of temperature.At last, photochromic material must seldom show fatigue or photolysis influence.Fatigue is the decline gradually of photochromic system performance, and its reason is transformed into other, and the ratio of the compound of dead end kind increases.
The compound exhibits photochromic effect that many types are arranged.Comprising pyrans, spiro-pyrans, fulgide ， Luo oxazine, etc.Usually the characteristic of spiro-pyrans is inferior to fulgide.Preferred The compounds of this invention is the Luo phenoxazine, and it all has good characteristic above-mentioned aspect all.The most preferred Luo phenoxazine of the present invention has the structure of formula I.
Wherein
R
1Be H, Cl, Br, alkyl, in conjunction with methoxyl, methoxyl, or trihalomethyl
R
2Be H or alkyl
R
3Be H or alkyl
R
4Alkyl for H or maximum 4 carbon atoms
R
5Be carboxy ethyl, cyano group propyl group, carboxyl methyl, methoxyl, or H.
The characteristic of photochromic compound depends on the interaction between they and their material of dissolution to a great extent.The photochromic compound reaction that is mixed with liquid solution is fast, and crystalline state the photochromic compound reaction or not slowly or fully.When they are dissolved in the stronger matrix of rigidity, because (structural change due to the A ← B) is limited, photochromic effect is obviously slowed down by photochemical reaction.In the prior art these compounds are placed rigid polymer as eyepiece.But the photochromic light meter that camera uses needs reaction more rapidly.Directly the dynamics that uses solution and use very pliable and tough polymkeric substance to obtain still is difficult to moulding, needs the antiseep sealing.Preferred forming method of the present invention comprises and places hydrophilic colloid to form the photography dispersion photochromic compound.Compound is dissolved in organic solution earlier, and then is scattered in water.The water of photochromic element dispersion comprises hydrophilic colloid.It can be gelatin or modified gelatin, the gelatin of phthalate, and the gelatin of oxidation, etc.Hydrophilic colloid also can comprise other water-soluble polymers or multipolymer, include but not limited to, poly-(vinyl alcohol), poly-(vinyl acetate/vinyl alcohol) of partial hydrolysis, hydroxyethyl cellulose, poly-(acrylic acid), poly-(1-vinyl pyrrolidone), poly-(Sodium styrene sulfonate), poly-(2-acrylamido-2-methane-sulforic acid), and polyacrylamide.Also can use the multipolymer of these polymkeric substance and hydrophobic monomer.
Photochromic compound also dissolves in higher boiling or the permanent solvent.Non-imposed ground also can use secondary solvent to help the dissolving of photochromic compound in permanent solvent.If the use secondary solvent can be by evaporation, washing, or dialysis removes, and spendable solvent comprises:
| Tricresyl phosphate (tolyl) ester | S-1 |
| Dibutyl phthalate | S-2 |
| N, N-diethyl dodecane acid amides | S-3 |
| N, N-dibutyl dodecane acid amides | S-4 |
| Three (2-ethylhexyl) phosphate | S-5 |
| Acetyl tributyl citrate | S-6 |
| 2,4-two-tert-amyl phenol | S-7 |
| 2-(2-fourth oxygen ethoxy) ethyl diethylstilbestrol ester | S-8 |
| 1, two (2 ethyl hexanoic acid) esters of 4-cyclohexyl dimethylene | S-9 |
| Ethyl acetate | S-10 |
Photography type disperse system can be coated in then in the thin layer on (photography) paper, cooling to be solidifying hydrophilic colloid, drying, and harden by the chemical crosslinking of gelatin.Various types of rigidizers all can be used for above-mentioned photographic element.Particularly two (vinylsulfonyl) methane, two (vinylsulfonyl) methyl ether, 1, two (vinylsulfonyl-acetylamino) ethane of 2-; 2,4-two chloro-6-hydroxyl-5-triazines, triacryl-triazine; and pyridine, 1-(4-morpholinyl-carbonyl)-4-(2-sulfoethyl)-, inner salt.Also can use the disclosed so-called snap action rigidizer of following document: U.S.Patent Nos, 4,418,142,4,618,573,4,673,632,4,863,841,4,877,724,5,009,990 and 5,236,822.
The thin slice of gained is convenient to processing very much, and can bonding agent be installed overleaf by cutting, or other job operations and make product.The photochromic performance of the above-mentioned thin slice of filming is very outstanding, has very fast dynamics, and this is because photochromic compound exists in solution effectively, is present in still to be scattered in the intradural a small amount of organic solvent.To provide the detailed job operation and the colorimetric characteristics of gained below.
The following example illustrates enforcement of the present invention.They are not to summarize all possible variation of the present invention fully.Unless otherwise noted, five equilibrium and number percent are by weight.
Embodiment
Press table 1 and make the photochromic compound disperse system.With photochromic compound, coupling solvent and auxiliary coupling solvent mix (part 1) at 50 ℃, and with glue, surfactant and water are in another container, also 50 ℃ of fusings.Two parts are merged, and in colloid mill, grind five times.Gained potpourri rotary evaporation is removed volatile matter, and secondary solvent (ethyl acetate) also adds the deionized water replacement.Can with gained disperse system fusing and with the water of requirement, gelatin, rigidizer and surfactant mix, and film at different thickness, obtain required performance.With this dispersant system the photography paper substrate on.This material can apply on paper substrate well, can not separate with paper substrate.Contain TiO
2Paper substrate very white, produce under blue chrominance signal that capacity sunlight produces down and the low light quantity colourless between contrast fine.Because film and paper substrate has optic the contact, the light that enters the photochromic front surface of filming reflects paper substrate, and photochromic layer produces two-way light (often for more multichannel) at least.This has just increased and to have absorbed the efficient that UV light causes change color.Also increased the visible density of the color that is produced.
Table 1: the preparation of photochromic compound disperse system
| 2%Aldrich 32254-7 1,3-dihydro-1,3,3-trimethyl spiral shell [2H-fen diindyl-2,3 '-[3H] naphtho-[2,1-b] [1,4] oxazine 4%N, N-diethyl dodecane acid amides 6% ethyl acetate | Part 1 is 50 ℃ of mixing |
| 6% gelatin, 0.6% surfactant (alkanol) balance deionized water | Part 2 merges and fusing at 50 ℃ |
With above-mentioned disperse system sample with about 15mg/ft
2(1.4mg/m
2) density of photochromic compound is coated on the photochromic paper substrate.Film is exposed to the following time of daylight of incident, and this sample has become blueness from white (color of photography paper substrate), and under 75 daylight, visual density is 0.4.When incident light was about 40-50fL, change color showed that single uses camera to obtain correct exposure.After removing light source, this film fades fully in time of 10 seconds being less than.Measurement is presented at removes light source in 7 seconds, color density reduce to former light to 10% of density.When being scattered in the acetic acid esters polymer film simultaneously, identical photochromic material, take off to 10% of original color density and need 10 times time and other compound needs-1000 times time as 1 ', 3 '-dimethyl-6-nitro-3 '-phenyl spiral shell-[2H-1-chromene-2,2 '-indoline].
This embodiment has also shown good fatigue properties.After under bright sun, exposing 8 hours, the dynamics of fading and the required incident exposure of generation clear signal no change.
With containing Tinuvin 1130 that ratio is 2: 1 Ciba-Geigy and the UV blocking-up ink overprint of Tinuvin292, the coating amount with 3% enters in the moisture bottom film with above-mentioned sample.This printing is to finish by carrying out serigraphy with required pattern on last institute disperse system is filmed.When being exposed to sunlight following time, the zone of printing ink keeps white, and Yin zone does not become tangible blueness rapidly, clearly forms required symbol or letter, tells the light that the cameraman has existed is enough to obtain high-quality photos.
Arrive this, the present invention is described in detail by particularly preferred scheme, still, obviously can carry out various variations or modification in essence spirit of the present invention and scope.
Claims (29)
1. a light activated element wherein comprises the photochromic chemical substance that is scattered in the hydrophilic colloid.
2. the light activated element of claim 1, wherein hydrophilic colloid comprises gelatin.
3. the light activated element of claim 1, wherein photochromic compound comprises the Luo phenoxazine.
4. the light activated element of claim 3, wherein the Luo phenoxazine is a formula I compound
Wherein,
R
1Be H, Cl
2, Br, alkyl, in conjunction with methoxyl, methoxyl, or trihalomethyl
R
2Be H or alkyl
R
3Be H or alkyl
R
4Alkyl for H or maximum 4 carbon atoms
R
5Be carboxy ethyl, cyano group propyl group, carboxyl methyl, methoxyl, or H.
5. the element of claim 1, wherein photochromic compound is selected from fulgide ， Luo oxazine, and spiro-pyrans (spiropyrines).
6. the element of claim 1 wherein further comprises host material, and this host material comprises reflectance coating.
7. the element of claim 6, wherein host material further comprises the ply of paper of resinizing.
8. the element of claim 6, its mesostroma are included in the bonding agent of the ply of paper outside coating relative with containing hydrophilic colloid layer.
9. the element of claim 6 wherein further comprises protective seam outside the Luo Fen of gelatin and the photochromic effect of tool oxazine layer.
10. the element of claim 6 wherein further comprises the mark on the matrix.
11. the element of claim 3, wherein Luo phenoxazine dispersion layer generally is transparent, unless be exposed under the light that can take without spark photograph.
12. the element of claim 9, the gelatin layer that wherein contains the Luo phenoxazine can become colorless from coloured in 1 minute.
13. the element of claim 3, wherein the Luo phenoxazine is selected from 5-chloro-1,3-dihydro-1,3,3-trimethyl-spiral shell [2H-indoles-2,3 '-(3H) naphtho-(2,1-b)-(1,4) oxazines] and 1,3-dihydro-1,3,3-trimethyl spiral shell-[2H-indoles-2,3 '-(3H) naphtho-(2,1-b)-(1,4) oxazine].
14. the element of claim 1 wherein has the UV Absorption material at least outside the photochromic compound part.
15. the element of claim 14, wherein the UV Absorption material is in pattern.
16. the element of claim 1, wherein photochromic material is printed in the pattern.
17. a single uses camera, wherein light activated element comprises the photochromic compound that is scattered in the hydrophilic colloid.
18. the camera of claim 17, wherein hydrophilic gel spare comprises gelatin.
19. the camera of claim 17, wherein photochromic compound comprises the Luo phenoxazine.
20. require 19 camera, wherein the Luo phenoxazine is a formula I compound
R
1Be H, Cl, Br, alkyl, in conjunction with methoxyl, methoxyl, or trihalomethyl
R
2Be H or alkyl
R
3Be H or alkyl
R
4Alkyl for H or maximum 4 carbon atoms
R
5Be carboxy ethyl, cyano group propyl group, carboxyl methyl, methoxyl, or H.
21. as the camera of claim 17, wherein host material comprises reflectance coating.
22. the camera of claim 17, wherein host material further comprises the ply of paper of resinizing.
23. the camera of claim 17, its mesostroma are included in the bonding agent of the ply of paper outside coating relative with gelatin layer.
24. the camera of claim 17 wherein further comprises mark on said matrix.
25. the camera of claim 19, wherein said Luo phenoxazine dispersion layer generally is transparent, unless be exposed under the light that can take without spark photograph.
26., can in the several seconds, become colorless from coloured comprising the photochromic layer of the gelatin that contains the Luo phenoxazine as the camera of claim 19.
27. the camera of claim 19, wherein photochromic material comprises and is selected from 5-chloro-1,3-dihydro-1,3,3-trimethyl spiral shell-[2H-indoles-2,3 '-(3H) naphtho-(2,1-b)-(1,4) oxazines] and 1,3-dihydro-1,3,3-trimethyl-spiral shell-[2H-indoles-2,3 '-(3H) naphtho-(2,1-b)-(1,4) oxazine].
28. the camera of claim 17, wherein said element have the UV Absorption material at least outside the photochromic compound part.
29. the camera of claim 17, wherein photochromic material is printed in the pattern.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US580,733 | 1995-12-27 | ||
| US08/580,733 US5747225A (en) | 1995-12-27 | 1995-12-27 | Light sensitive device |
| US580733 | 1995-12-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1159574A true CN1159574A (en) | 1997-09-17 |
| CN1089451C CN1089451C (en) | 2002-08-21 |
Family
ID=24322322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96123411A Expired - Fee Related CN1089451C (en) | 1995-12-27 | 1996-12-27 | Photochromism explosure meter |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5747225A (en) |
| EP (1) | EP0783130B1 (en) |
| JP (1) | JPH09189983A (en) |
| CN (1) | CN1089451C (en) |
| DE (1) | DE69619956T2 (en) |
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| SE525673C2 (en) * | 2003-08-13 | 2005-04-05 | Peltor Ab | Indicator for aging of plastic articles and protective helmet including an indicator device |
| JP2007512526A (en) * | 2003-11-20 | 2007-05-17 | フレッシュポイント・ホールディングス・ソシエテ・アノニム | Method and system for measuring state of time temperature index |
| US9835498B2 (en) * | 2003-11-20 | 2017-12-05 | Freshpoint Quality Assurance Ltd. | Method and system for determining the condition of a time-temperature indicator |
| US8267576B2 (en) | 2004-11-08 | 2012-09-18 | Freshpoint Holdings Sa | Time-temperature indicating device |
| DE102006034854A1 (en) * | 2006-07-25 | 2008-01-31 | Ovd Kinegram Ag | A method for generating a laser mark in a security document and such a security document |
| EP2102615B1 (en) | 2007-01-11 | 2011-12-28 | Freshpoint Holdings SA | Time temperature indicator |
| US7570423B2 (en) * | 2007-01-25 | 2009-08-04 | Hewlett-Packard Development Company, L.P. | Projection screen |
| US7718325B2 (en) * | 2007-06-13 | 2010-05-18 | Xerox Corporation | Photochromic material, inkless reimageable printing paper, and methods |
| US7572569B2 (en) * | 2007-06-13 | 2009-08-11 | Xerox Corporation | Inkless printing paper and method |
| US7588878B2 (en) * | 2007-06-13 | 2009-09-15 | Xerox Corporation | Inkless printing paper and method |
| US7655366B2 (en) * | 2007-06-13 | 2010-02-02 | Xerox Corporation | Inkless reimageable printing paper and method |
| US7666558B2 (en) * | 2007-06-13 | 2010-02-23 | Xerox Corporation | Inkless reimageable printing paper and method |
| US7645558B2 (en) * | 2007-06-13 | 2010-01-12 | Xerox Corporation | Inkless reimageable printing paper and method |
| US7541119B2 (en) * | 2007-06-13 | 2009-06-02 | Xerox Corporation | Inkless reimageable printing paper and method |
| US20080311493A1 (en) * | 2007-06-13 | 2008-12-18 | Xerox Corporation | Inkless reimageable printing paper and method |
| US7582398B2 (en) * | 2007-06-13 | 2009-09-01 | Xerox Corporation | Inkless reimageable printing paper and method |
| US7569316B2 (en) * | 2007-06-13 | 2009-08-04 | Xerox Corporation | Inkless reimageable printing paper and method |
| US7867672B2 (en) * | 2007-06-13 | 2011-01-11 | Xerox Corporation | Reimageable paper protected against UV light |
| US7572560B2 (en) * | 2007-06-13 | 2009-08-11 | Xerox Corporation | Inkless reimageable printing paper and method |
| US7852366B2 (en) * | 2007-06-13 | 2010-12-14 | Xerox Corporation | System and method for printing reimageable transient documents |
| US7553603B2 (en) * | 2007-06-13 | 2009-06-30 | Xerox Corporation | Inkless printing paper and method |
| US20090162120A1 (en) * | 2007-12-21 | 2009-06-25 | Manico Joseph A | Printer and printing method using receiver medium having adjustable properties |
| US7875314B2 (en) * | 2007-12-21 | 2011-01-25 | Eastman Kodak Company | Method for using receiver medium having adjustable properties |
| US8968662B2 (en) * | 2008-06-23 | 2015-03-03 | Freshpoint Quality Assurance Ltd. | Time temperature indicator |
| FR2933785B1 (en) * | 2008-07-11 | 2010-09-03 | Thales Sa | PHOTOCHROMATIC MATERIAL |
| US7645560B1 (en) | 2008-09-08 | 2010-01-12 | Xerox Corporation | Inkless reimageable printing paper and method |
| US8728685B2 (en) * | 2009-06-25 | 2014-05-20 | Sabic Innovative Plastics Ip B.V. | Method of making holographic storage medium |
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| US3291604A (en) * | 1963-02-01 | 1966-12-13 | Eastman Kodak Co | Process for creating and subsequently transferring an ionic photochromic image |
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| JPH0726046B2 (en) * | 1987-02-10 | 1995-03-22 | 株式会社パイロット | Photochromic ink |
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| JPH05142700A (en) * | 1991-11-20 | 1993-06-11 | Konica Corp | Photographic unit |
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| US5532104A (en) * | 1993-08-19 | 1996-07-02 | Olympus Optical Co., Ltd. | Invisible information recording medium |
| JPH07159877A (en) * | 1993-12-01 | 1995-06-23 | Konica Corp | Camera |
| US5555046A (en) * | 1994-12-23 | 1996-09-10 | Eastman Kodak Company | Flash indication aid for cameras with manual flash |
-
1995
- 1995-12-27 US US08/580,733 patent/US5747225A/en not_active Expired - Fee Related
-
1996
- 1996-12-14 DE DE69619956T patent/DE69619956T2/en not_active Expired - Fee Related
- 1996-12-14 EP EP96203547A patent/EP0783130B1/en not_active Expired - Lifetime
- 1996-12-26 JP JP8348743A patent/JPH09189983A/en active Pending
- 1996-12-27 CN CN96123411A patent/CN1089451C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE69619956D1 (en) | 2002-04-25 |
| DE69619956T2 (en) | 2002-11-07 |
| EP0783130A1 (en) | 1997-07-09 |
| US5747225A (en) | 1998-05-05 |
| JPH09189983A (en) | 1997-07-22 |
| EP0783130B1 (en) | 2002-03-20 |
| CN1089451C (en) | 2002-08-21 |
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